This development follows the recent collapse of Wilko, the discount homeware chain.
It had been under the ownership of the Wilkinson family for decades, placing 12,500 jobs in line.
While the deal covers "up to" 71 Wilko outlets, the final count will be determined through negotiations with each site's landlords to finalize lease terms.
Initially, the HMV owner sought a rescue deal to save 400 branches, but it eventually collapsed earlier this week.
Consequently, PwC announced the impending closure of all Wilko stores by early October, resulting in 9,100 employees letting go.
B&M, another discount retailer, had previously signed an agreement to acquire 51 Wilko stores.
However, whether staff at these branches will be retained or rehired remains uncertain.
In total, the 122 sites encompassed in the deals with Pepco and B&M employ over 3,200 staff.
Joint administrator Edward Williams said: "Alongside the previously announced agreement with B&M, we're confident this sale will create a platform for future employment opportunities for people including current Wilko team members at up to 122 locations.
"We will continue to engage with other retailers around any interest in other Wilko sites and are confident of completing a sale of the brand and intellectual property within the coming days."
A Poundland spokesman said the stores involved in the deal are primarily situated in areas where the company currently has a "limited presence."
He added: "The lease assignments are expected to be completed in early Autumn, enabling these stores to join Poundland's existing 800-plus UK estate and open in the important fourth calendar quarter of 2023."
The announcement coincides with the final day of operations for 24 stores in the initial phase of mass closures.
An additional 28 shops are scheduled to close at the end of the following day.
Wilko faced insurmountable challenges, including inflationary pressures, rival competition, and supply chain disruptions, leading to its administration.